Disazo dyestuffs and their metal complex compounds



United States 2,824,866 DISAZO DYESTUFFS AND THEIR NETAL COMPLEXCUMPOUNDS Hans Ischer and Lukas Schneider, Basel, Switzerland,

assignors, by mesne assignments, to Saul & Co., Newark, N. 1., asnominee of Fidelity Union Trust (loinpany, executive trustee underSandoz trust No Drawing. Application December 13, 1354 Serial No;474,974

Claims priority, application Switzerland December 18, 1953 7 Claims.(Cl. 260-143) The present invention relates to valuable disazo dyestufisand their metal complex compounds.

It is known from the U. S. Patent No. 2,623,873, that the individualmembers of a new group of disazo dyestufis are obtained by coupling anappropriate diazotized aminoazo dyestuif which corresponds to theformula wherein R represents an aromatic radical of the benzene ornapthalene series which, in ortho-position to the azo group, bears asubstituent which is capable of metal complex formation, x stands for Hor 80 1-1, one 3 stands for CH and the other y stands for Nl-l with anaminohydroxy-naphthalene sulfonic acid which corresponds to the formulaH O as N H-aeyl wherein the naphthalene nucleus may carry a further SO Hgroup.

It has now been found that also valuable disazo dyestuffs and theirmetal complex compounds are obtained,

when using as aminoazo dyestufifs of Formula I for the preparation ofthe diazo compounds, aminoazo dyestuifs wherein x is a chlorine atom,and R stands for the radical of an aminobenzene which bears analkylsulfonyl-, cycloalkysulfonyl-, aralkylsulfonylor arylsulfonyl group(for example 402-CH3, 402C Hu, SOZ.CHZVC6II5, SO C H and also carries,in ortho-position to the amino group a substituent which is capable ofmetal complex formation (for example OH, OCH -COOi-l,

--OCH COOH), and/or as end-positioned azo components (a) asymmetricureas which correspond to the formula 2,824,866 Patented Feb. 25, 1958are free from acyiamino groups, which compounds couple in ortho-positionto the hydroxy group.

T he new disazo dyestufis correspond, in metal-free state, to theformula E e: (IV) wherein R stands for an aromatic radical of thebenzene or napthalene series which, in ortho-position to the azo group,bears a substituent which is capable of metal complex formation, zstands for hydrogen, chlorine or SO H, one w stands for CH and the otherw stands for the radical of an azo component connected with nucleus A byan azo bridge, which azo component radicalwhen R is the radical of anaminobenzene which carries an a1kysulfonyl-, cycloalicylsulfonyh,aralkylsulfonylor arylsulfonyl group and, in ortho-position to the aminogroup, a substituent which is capable of metal complexformation-corresponds to the formula wherein z has the aforesaidsignificance, or is a radical of Formula ill, or the radical of acompound of the aliphatic or heterocyclic series which is capable ofcoupling because of the presence of the cool group -C(OH)=CH, or is theradical of a couplable compound selected from com pounds of the seriesconsisting of hydroxybenzenes, hydroxynaphthalenes andhydroxynaphthalene sulfonic acids which are free from acylamino groups,which compounds couple in ortho-position tothe hydroxy group, and-when Rstands for the radical of an aminobenzene which contains, inortho-position to the amino group, a substituent which is capable ofmetal complex formation, but is free from alkylsulfonyl-,cycloalkylsnlfonyl-, aralkylsuifonylor arylsulfonyl groups-is a radicalof Formula ill, or the radical of a compound of the aliphatic orheterocyciic series which is capable of coupling be cause of the coolgrouping -C(Ol-l) =CH, or the radical of a couplable compound selectedfrom compounds of the series consisting of hydroxybenzenes,hydroxynaphthaienes and hydroxynaphthalene sulfonic acids which are freefrom acylamino groups, which compounds couple in ortho-position to thehydroxy group.

The new disazo dysetuifs, when they are in the metalfree state, dyecotton and fibers of regenerated cellulose in orange, red to violetshades, which are rendered fast to washing and to light by treatmentwith metal-yielding, for example copper-yielding agents. In so far assolubility permits, the disazo dyestuffs can also be converted insubstance in per se known manner into the corresponding metal complexcompounds, particularly into the copper and nickel complex compounds,whereby very light-fast direct dyestuffs are obtained. These also dyethe aforesaid fibers in orange, red to violet shades which are fast towashing and to light. With respect to the comparable products of theaforesaid patent, the disazo dyestufis of the present invention possessin part essentially improved solubility in water. Their dyeings arecharacterized, relative to those of the known dyestufis by clearer tonesand in part by better fastness to washing. It is possible to favorablyinfluence the dyeing properties of the dyestud by using their: in theform of mixtures. Thus, for

' l afterecoppering process in redshades of good fastness to light andtowashing. a a r example, a mixture of 60 parts by weight of .the disazodyestuff disclosed in Example 28, infra, with 40 parts by weight of thedisa zo dyestuff according to Example 30 infra has 'somewhat'supericr'dyeing-properties as compared with the individual components. V

I? Thene'w dyestuifs-are advantageously prepared by coupling theindirectly diazotized aminoazo dyestufis with I ear-om Ho3s A in the azocomponents, preferably in weakly alkaline me- "Typical ;presentlypreferred embodiments of thetinven "'tion are 'setforth by wayofillustration in the following examples. n these examples, parts are byweight', peif centa'ges areby-weight, and temperatures are in degreesfcen'tigrade. 7 I V 7 EXAMPLE 1 59 'parts of the mono'sidiumsalt of theaminoazo dyestufi, obtained by alkaline coupling ofdiazotizedl-hymethy1-4- amino) benzoylainino--hydroxynaphtha1ene- 7-sulfonic acid,are dissolved in 1100 parts oi water with --addition of 20 parts ofaqueous 'sodiumvhydroxide soluation of 3 O%-s,tre n gth. 24 ,partsofaqueous sodium nitrite solution'of strength are added to the resultantsolution, Whichds 'then cooled to .a temperature oft5 by pmea'ns' of-ice,after which IOQ parts of hydrochloric acid {of 30% strength arequickly run in while stirringlthorpughly. After stirring the mixture for6 hours at a tern ,perature' of 10-15.", the ,diazotization is finished;the resultant suspension is ,then combined in the presence of excesssodium carbonate with an aqueous solution Of 739 parts 'offsbdium'2fbenzoylaminoe5 hydroxynaph thalene 7 slilfonate. The. new disazo''dyestu'ff forms 'instantaneously.- Itris precipitated from the ,hotsolution by means of sodium chloride, and is then filtered ofijan'didried. this a dark powder which dissolves in watertend "in concentratedsultonie iaeifd with blue-red coloration;

V a The new dyestuff, which corresponds to the formula r Qdyes cotton:andlfibers' of regenerated cellulose the mEXAMPLEhZ V solution isrendered alkaline vby means ot 100 parts 11f aqueous ammonia of strengthand then at 80 and in the course of minutes asolutionof 25 parts ofcrystalline copper sulfate in l00 .parts of water is run in. The pp omplx ,fc ni icn o heQd-QiQYQIQKY dyestufi takes placeyeryrapidly; ,Theinewdyestuifwhich corresponds to theformula' e c e r a sore a cai n-031 .isthereupon salted outyfiltered of! and 1t -;dis-

tsolves with red coloration in water and dyes cotton and fibers ofregenerated cellulose .in bluish ired shades iof excellent fastness tolight and good tastness-to washing,

' The latter can be furtherim'provedtby' an after treatment 7 of thedyeings with an optionally basic, cation active copper complex compound.I

A meta'lliferous disazodyestufi more even fasterto; washing is dbta'inedwhen, in the present example, the

metallization of the disazo compoundiscartie'd out with 15.5 parts ofnickel sulfate instead of 25 tpartsofcopper sulfate EXAMPLEB The aminoazo dyestulf," "obtained' by coupling 18.7" 7

parts of diazotized lehydroxy-2-amino-4methylsulfonylzoylamino-5-hydroxynaphtha1ene 1,7-disulfonic acid 'in'a'medium rendered alkaline with sodium bicarbonate is stirred into 300parts .0; water. 7 parts of sodium nitrite are added to the suspension,after which 30 parts of hy-' drochloric acid of 30% strength are addedalleat onetime i at 8 and while stirring thoroughly; 7 Thefdiazotization v 7 is terminated in about 2 hours. The obtained diazosusypensionis run, at-10-'1-5, into a solution of '4 1.5 ans-o5-hydroxy-7-sulfonaphthyl(2)-carbaminic acid-(4'-a'eetylamino)-phenylamide and 40'parts of sodium carbonate 1 in "filo-parts ofwater. ,"The coupling to form -the disazo *dyestulf takes place veryrapidly; At the'end 'o'f 2 hours,

97 g parts ofzthe disaizo idyest ufi, obtained" according to the data ofExample by gcpupling diaz'otized l-hydroxy 2 amino-F 4methylsultcnylbenzene with 2-(3f- ;n g 1;l 1y1-4' amino-)bnzoyla'mino-Shydroxynaphthalenecaxbethflxyarn nq i-thydroxynaphthalene 7-:ulfonic 7 tlflvdisulfonic acid, ,vfollowed byiurther'diazotization oi re u ta tkamiomo a' "dy tu f a qupli *With V w acid, are'dissolved in 3000 parts; ofwater lat 80f The a sodium chloride;

the disazo dyestufi isflsalted out of the -solutionland' I Forconversion thereof into the cppper complex comd of water at The solutionis cooled down to 50-609, 200 parts of aqueous-ammonia of '25% strengthare added, and while maintaining thelast mentionedtemper- V iature ofsolutionof 25 parts of crystalline copper sulfate;

in 500 parts of waterisyadded in the course @530 minutes,

As soon as excess copper sulfate can be detected in 'a salted-tout" testspecimen ,theiiresultant copper vctmaplex Icomp'ound of the vdisa'zodyestufi is precipita'tedfromjthef' l l l metalliza'tion solution hy thefaddition of 3130: *partsj 'ofand is then filtered oif and dried'under;

pound, the obtained dyestufi' is dissolved in 3000 parts reducedpressure at 90. The copper-containing disazo perature 30 parts ofconcentrated hydrochloric acid are.

dyestufi which corresponds to the formula added and the mixturestirred'for about 2 hours. The

sour om no: NH-C O-NH NH-ooom SOs-CH: H: NH-CO N=N obtained diazosuspension is then run, at 5 to into a solution of 41.5 parts of5-hydroxy-7-sulfonaphthyl(2)- carbaminic acid-4-acetylamino)-phenylamideand 40 parts of sodium carbonate in 500 parts of water. The

is soluble with red coloration in water and dyes cotton, and fibers ofregenerated cellulose in red shades of excellent fastness to light andgood fastness to Washing. The latter can be further improved by aftertreating the cou lin roceeds ver ra idl after 2 hours the mass 1s dyemgswlth an Opuonauy basic canon-acme copper wari ned t t a 70, and the isao dyestuif which has gone cmplex compounfi' p into solution and whichcorrespondsto the formula p i 5 cm Hots NH-C O-NHONH-COCH:

som H038 NHCO-N=N QM at H H0 7 I EXAMPLE 4 is salted out with parts ofsodium chloride, filtered ofi In order to prepare the nickel complexcompound of 35 and dried at 90 .mder reduced Q It is i the diazodyestufi according to Example 3, a process brown powder which dissolveswith red coloration in alogous to that employed in the coppering iscarried out water and dyes cotton and fibers of regenerated celluloseThe disazo dyestufi is dissolved in 3000 parts of water In Clear redshaqes which are changed to red'vlolet by at After cooling the solutionto 200 parts of aftertreatment with copper salts and thereupon becomeaqueous ammonia of 25% strength are added and then, 40 fast to washingand to light at the same temperature, a solution of 15.5 parts of nickelThe dlsazo dyesmfl PrePaTed acc1'dmg the Present lf t in 100 parts fWater is run in. The nickel example can also be converted in substancento a water Flex compound f the disazo dyestufi forms very rapidlysoluble metal complex compound, especially into thecopas can be observedby the change of the color of the Per mckel complex P which dyes{enulose solution from violet-red to red. Upon completion of the ,5fibers-m blue'red shacks Whlch are Very fast to hghtaddition of thenickel sulfate solution, the nickel-con- EXAMPLE 6 taining disazodyestuff is salted out, filtered off and dried.

It corresponds. to the'formula The aminoazo dyestuif, obtained bycoupling 18.? parts son; on: Hogs NH-C 0-NH-C N110 0 on,

SO:CH: HOaS NH-CO N =N N=I:I H

l -1 no and dissolves with red coloration in water and dyes cotofdiazotized 1-hydroxy-2-amino-4-methylsulfonylbenzene ton and fibers ofregenerated cellulose in brownish red With 37.2 parts of2-(4-amino-3-methyl)-benzoylshades with excellent fastness to light andgood fastness amino-5-hydroxynaphthalene-7-sulfonic acid in a medium towashing, which latter can be further improved by rendered alkaline withsodium carbonate, is stirred into aftertreating the dyeing with anoptionally basic, cation- 400 parts of water. 7 parts of sodium nitriteare added active copper complex compound. to the suspension, and thelatter is then cooled to 6-8".

At this temperature and while stirring, 30 parts of con- EXAMPLE 5centrated hydrochloric acid are added and stirring is The aminoazodyestuff, obtained by coupling 18.9 parts continued for approximately 2hours. The diazo susof diazotized l-hydroxy-2-aminobenzene-4-sulionicacid pension is then run, at 15-20", into a solution of 15 parts with37.2 parts of 2-(3'-methyl-4-amino)-benzoylaminoof Z-hydroxynaphthalene,6 parts of-sodiurn hydroxide 5-hydroxynaphthalene-7-sulfonic acid in amedium renand 30 parts of sodium carbonate in 400 parts of water. deredalkaline with sodium carbonate is stirred into 400 The disazo dyestufiforms very rapidly. It is salted out 7 parts of water. 7 parts of sodiumnitrite are added to of the warm solution by the addition of'sodiumchloride the suspension which is then cooled to 8. At this term and isthen filtered oflf and dried at under reducedamino-S-hYdroxynaphthalene-7-sulfonic*acid in la'rne'iliu'rm with thedata of the preceding example. The diazo suspension isrthen run, at15+2O, into a'solution of 30.5 30

parts of sodium carbonate in SOOparts of water' The a disazodyestufiforms very rapidlyi At the en d of about i pound; the processaccording toExample 3 is followed;

sot-oar 1103s assesses ass-same; away-6 mg wliiehFeQrresQOnds-RQ "tli Qis ablack powder which dissolves with red coloration can be preparedafter the manner describedinlixample in water and dyes cotton and fibersof regenerated cellu- 4. It corresponds to the formula a a V HC j's'oa-omaoisi- 1 anima I.

5156 bythe'afterscoppefing P 'l a dissolves with red colorationiniwater, and "dyes cotton EXAMPLE '7 and fibers of regeneratedcellulose in red shades with a e aminoazo, dye'stufi obtained ycouplingivlsj pans: good fastness to light and to washing. The latterpropoff' dia'z'otize'd V 1-hydroxy-Z-amino 4=mcthylsulfonylhem" zeneWlth 37.2 parts of 2-(4 am no-3 rnethylkbenzoyl- 25 wmpiexcompoundi vrendered alkaline with sodium carbonate, is stirred into 400 mm of waterand then diazotized, in accordance 'yresent mvennran am sek'fiotth m7summan'zfid farm in the following table; The sai'd disa'zo dyestuffs areparts of1-hydroxynaphthalene-3,8-disulfonic'acid'and 40 7 lhourslit 'is'precipitated 'from'thewarrh, solution'by the U 7 b a i it a Bath; v a 7h addition of sodium chloride and is thenfilt'ered'ofi. 35 sme at a poppg "process; Vere f a Forconversionlthereof into the copper-1 complexcom- 7 The resultant copper-containing disazo dyestufl c'orree sponds tothe formula 1 in column 4, are those which are flpp redf ofithe'fiberi rV j .1 V '7 andldissolves'in water with-red colorationand dyes 'cot- Bdes tes the disazo dyestuas1whiehqarecopp z n ton and fibers ofregenerated cellulose in red shades of substance, whlle C designatesmckel complex compounds. excellent fastness to light and 'good fastilessto washing. a rm a of p y, t -3- hyl)- The latter property can befurther considerably improved. benzoylamlno 5 7 hydroxynaphthalene7-sulfonic acid, by aftertreating"the dyeingswith anoptionallybasiqcatwhich 'is'used in most cases-for making the aminoazoion-active copper complex compound. V i J V 'dyestufi of Formula I, isdeslgnated as AMBQS;

7' i Tabl EL 7 1 7 a (3) [(4) (5)" 2-aminobenzene-1-carhoxylicacidQAMBOS5-hydroxy-7-sulfonaphthyl(2)-carbaminic A V V a 7 Vacid-(4-acetylamiuo)-phenylamide. V n 2 ;5'-"hydroxyj-7sulfonaphthyltzhcarbaminic, A1 7 a a r V acid propylamide., 1 i V 7 do 1-shydroxy-7-sulfonaphthyl(2)-earbaminie- A aeidbenzylamide" y .1hydroxy: 2 aminohehzene =4 5 hydroxy 7 sulionaphthylflkcarbaminie C(3-methyl-4-amino)-henzoylam '5-hydroxyl aeid-(fi-benzoylamino)phenylamide: 7 v naphthaIene-IJ-disulfonic acid, 0: '1 a y j, r J t t12".- 1-hydr0xy-2-aminobenzene=4 sulfo cn'cid amide 5 hydroxy 7su1ionaphthyl(2)-carbaminie Q s -canbarninic Lacid-flfl-acetylamino)-phenylamide. 8+ hydroxy- 6sulI0napnthyl(2)-carbamim aerd-(4'-acetylaminol-phenylamitie: V 5-hydroxy 7; suhonapnthymlrcanbam aoid-( l -phenyDmhenylaniide; I e -5;hydr 9 xy. 7 sulfonaphthyltgl-earlr 1 acid. methylamide; t

ewe emp dz de i erty can be considerably improved by aftertreating the'V dyeings with an optionally basic, cationactive copper 1 A Additionaldisazo' dyestuifs obtainable according to characterized in sucmtableflby the 'aminoazo dyestufi s' (column 2) and ac components(columnfi) used in; making the'dyestufis, and also by the shade (column5)f of the dyeings tpreparedrwithpthemew dyestuffs; These 7 disazodyestuffs arebrought onf the fiber either by the their solubiliity illf\ilatergperniits they'are' used "for-"dye ingin' the term-of theircep'p'erj orfnichel'eomplex com= pounds: Disazo' dyestuffs which aredesignated by; A 7

Having thus disclosed the invention, what is claimed hydrogen, loweralkyl, cyclohexyl, ben'zyl, plie'nyl, acetylis:

1. A member selected from-the group consisting of disazo dyestuffs whichcorrespond to the formula penylranimosulfonylphenyl 'sulfophenyl and f iV V 6 and R being a member selected from the group consisting on no,NH-OO N=N R N=N NH-w and the complex copper and nickel compoundsthereof, of hydrogen and methyl. 7 V V wherein the CH on nucleus A is inone of the Said 2. A disazo dyestufi which corresponds to the formulapositions 3 and 4 of the latter and the gmupmg wherein the CH on thenucleus A is in one of the 0H positions 3 and; of the latter and thegrouping NH-u e 1 Hmsis in the other of the positions 3 and 41R standsfor a member selected from the group consisting of (ayatomatic radicalsof the benzene and naphthalene series which H01 contain inortho-position to the azo group a substituent 35 capable ofmetal-complex formation and alsocontain a substituent selected from theclass consisting 'of lower'itl if. alkyl sulfonyl, cyclohexylsulfonyl,benzylsylfqnyland r mononuclear arylsulfonyl, androf tb), aromaticradicals is i n the other of the said positions 3 and 4; R stands for ofthe benzene and naphthalene;"cries, whichcontainimgo a member selected;from the group consisting of aroortho-position to the azo group asubstitue'nt capaolewf matic radicals of the benzene and the naphthaleneseries metalrcomplex formation but 6 free m bt l1l dfi Tfiwhich containin ortho-position to the azo group a subslllfonyl g p Z Stands a'aqnPw-aglcgte 5 -stitutent ,capable of metal-complex formation and alsogroup consisting of hydl'cfgeni 3- 5fid containe substituent selectedfrom the class consisting w stands R contams @subsmued sun-my} 5 45 oflower alkylsulfonyl, cyclohexylsulfonyl, benzylsulfonyl acyl radlcalselected fi the 'conslstmg i and mononuclear arylsulfonyl; 2 stands foramember ralhcals of saturatfdh i i g g i selected from the groupconsisting of hydrogen, chlorine fi g the lower 3. p any c an 33 2:: and40 11; and acyl stands for a member selected from a 1p am series ta ma 8o mononuc ear aroma the group consisting of radicals of saturated andunsatucarbox lic acids, radicals of s ubstitued carbamic acids thesugstimems being chose-n from thc class c n 0 rated monocarboxyhc acidsof the lower aliphatic, phenylof lower alkyl cyclohexyl benzyl, phenyl,acgtylaminw aliphatic and phenoxy-aliphatic series, radicals of mondphenyl, propionylaminophgny'l, benzoylaminophgfiyl? nd. nuclear aromaticmonocarboxylic acids, radicalsof subo lf ylph l, ulfo h nyl d diphgnylyljpesidugs stituted carbamlc acids, the subsntuents being chosen andstands, when R is free from substitu'ed 'sulfonyl 55 from the classconsisting of lower alkyl, cyclohexyl, bengroups, for the grouping zyl,phenyl, acetylaminophenyl, propionylaminophenyl,

aminophenyl, propionylamino phenyl, benzoylamino- HI Ibenzoylaminophenyl, aminosulfonylphenyl, sulfophenyl' CQ N/ anddiphenylyl.

3. The disazo dyestufi which corresponds to the for 0 mula om HO;Nil-COO SOs-CH: H018 NH-CO N=N 6 R being a member selected from thegroup consisting of

1. A MEMBER SELECTED FROM THE GROUP CONSISTING OF DISOZO DYESTUFFS WHICHCORRESPOND TO THE FORMULA